Patent GB-1061988-A (GB)
Title: Copolymers and coating compositions containing the same
IPC: C08F18/12
Filed: 1963-12-03
Abstract: Esters of formula <FORM:1061988/C2/1> where X is an organic radical free from polymerizable groups and containing at least one hydroxyl or carboxyl group and Y and Z are each hydrogen, halogen, hydroxyl or C1- 3 alkyl are prepared by reacting the alcohols with the appropriate acids, anhydrides or lactones. Examples describe the preparation of the mono-allyl esters by reacting allyl alcohol with chlorendic anhydride, tetrachlorophthalic anhydride, glutaric anhydride, phthalic anhydride, succinic anhydride, trimellitic anhydride, adipic acid, b -propiolactone and glycolic acid; the monomethallyl esters by reacting methallyl alcohol with glutaric anhydride and trimellitic anhydride; and mono (1-penten-3-yl) glutarate by reacting 1-penten-3-ol with glutaric anhydride.ALSO:Copolymers comprising a major molar proportion of at least one ester of formula <FORM:1061988/C3/1> where A is C1- 3 alkyl and B is hydrogen or methyl, and a minor molar proportion of at least one ester of formula <FORM:1061988/C3/2> where X is an organic radical free from polymerizable groups and containing at least one hydroxyl or carboxyl group, and each of Y and Z is hydrogen, halogen, hydroxyl or C1- 3 alkyl, may be prepared by polymerization in organic solvents in the presence of catalysts, e.g. benzoyl peroxide and azodiisobutyronitrile.  Specified monomers which may be used with vinyl and isopropenyl acetates, propionates and butyrates are allyl urea, diallyl melamine, acrylamide and methacrylamide which may be alkylolated or alkylolated and etherified, hydroxyethyl and hydroxypropyl methacrylates, propyl, butyl and 2-ethylhexyl acrylates, vinyl stearate, vinyl chloride, vinylidene chloride, dibutyl maleate, dibutyl fumarate and allyl isocyanate.  Examples of the second class of esters are the allyl, methallyl, chloroallyl, hydroxyallyl and 1-penten-3-yl esters of succinic, glutaric, adipic-pimelic, suberic, azelaic, sebacic, phthalic, isophthalate, tetrachlorophthalic, mellitic, trimellitic, chlorendic, glycolic, tartaric, lactic, b -hydroxypropionic, citric, carbamic and hippuric a acids.  Carboxyl containing copolymers may be rendered water-soluble by at least partial neutralization.  The copolymers may be mixed with aminoplast resins and polyepoxides, optionally together with cross-linking catalysts, to give coating compositions. Specified aminoplasts are condensates of urea, melamine, dicyandiamide formoguanidine, ammeline, 2-chloro - 4,6 - diamino - 1,3,5 - triazine, 2-phenyl-p - oxy - 4,6 - diamino - 1,3,5 - triazine, 6 - methyl - 2,4 - diamino - 1,3,5 - triazine, 2,4,6 - trihydrazine - 1,3,5 - triazine and 2,4,6 - triethyl triamino-1,3,5-triazine with formaldehyde, acetaldehyde, crotonaldehyde, acrolein, furfural, benzaldehyde hexamethylene tetramine, paraldehyde, paraformaldehyde and trioxymethylene, optionally etherified with methyl, ethyl, isopropyl, butyl, isobutyl, ethylhexyl, lauryl and stearyl alcohols. Specified polyepoxides are 4-vinyl cyclohexene dioxide, diallyl ether dioxide and polymers thereof, polyallyl glycidyl ether, epoxidized polybutadienes, epoxidized styrene/butadiene copolymers, glycidyl acrylate and methacrylate copolymers and the resinous condensates of epichlorhydrin with glycerol and diphenylolpropane. Specified catalysts are sulphuric, phosphoric, hydrochloric, n-butyl phosphoric, toluene sulphonic, and trichloracetic acids, boron trifluoride etherate, organic amines and quaternary ammonium bases. Many examples are given including the preparation of copolymers of vinyl acetate with monoallyl succinate; monoallyl chlorendate; monoallyl tetrachlorophthalate; monoallyl glutarate; monoallyl phthalate; vinyl stearate and monoallyl adipate; vinyl stearate and monoallyl trimellitate; vinyl stearate and monoallyl glutarate; vinyl stearate, monoallyl glutarate and diallyl melamine; vinyl stearate, monoallyl glutarate and allyl carbamate; 2-ethylhexyl acrylate, acrylamide and monoallyl glutarate; vinyl stearate, monoallyl glutarate and allyl urea; vinyl 2-ethylhexoate and monoallyl glutarate; vinyl 2-ethylhexoate and monoallyl trimellitate; allyl lactate; allyl glycolate; allyl b -hydroxypropionate and dibutyl maleate; allyl lactate and monoallyl trimellitate; allyl glycolate and monoallyl trimellitate; monomethallyl glutarate; monomethallyl trimellitate; mono-(1-penten-3-yl)glutarate; isopropenyl acetate and monoallyl glutarate; and vinylidene chloride and allyl glycolate; and of vinyl butyrate with monoallyl glutarate; and the preparation of coating compositions comprising these copolymers and rutile titanium dioxide; hexamethylol melamine hexamethyl ether, methylated urea/formaldehyde condensates, ethylated urea/formaldehyde condensates or methylated melamine formaldehyde resins together with toluene sulphonic acid; or epichlorhydrin-diphenylolpropane condensates together with tertiary amines.ALSO:Substrates, e.g. primed steel panels, may be coated with compositions comprising copolymers of a major molar proportion of at least one ester of formula <FORM:1061988/B1-B2/1> where A is C1-3 alkyl and B is hydrogen or methyl, and a minor molar proportion of at least on ester of formula <FORM:1061988/B1-B2/2> where X is an organic radical free from polymerisable groups and containing at least one hydroxyl or carboxyl group and Y and Z are p  each hydrogen, halogen, hydroxyl, or C1-3 alkyl, together with aminoplast resins or polyepoxides, optionally together with cross-linking catalysts such as acids and organic amines and quarternary ammonium bases.  Many suitable comonomers, aminoplasts, polyepoxides and catalysts are specified and examples describe the coating of primed steel panels with aqueous and organic solvent based coating compositions comprising copolymers of vinyl acetate with monoallyl succinate; monoallyl chlorendate; monoallyl tetrachlorophthalate; monoallyl glutarate; monoallyl phthalate; vinyl stearate and monoallyl adipate; vinyl stearate and monoallyl trimellitate; vinyl stearate and monoallyl glutarate; vinyl stearate, monoallyl glutarate and diallyl melamine; vinyl stearate, monoallyl glutarate and allyl carbamate; 2-ethylhexyl acrylate, acrylamide and monoallyl glutarate; vinyl stearate, monoallyl glutarate and allyl urea; vinyl 2-ethylhexoate and monoallyl glutarate; vinyl 2-ethylhexoate and monoallyl trimellitate; allyl lactate; allyl glycolate; ally b -hydroxypropionate and dibutyl maleate; allyl lactate and monoallyl trimellitate; allyl glycolate and monoallyl trimellitate; monomethallyl glutarate; monomethallyl trimellitate; mono(1-penten-3-yl)glutarate; isopropenyl acetate and monoallyl glutarate; and vinylidene chloride and allyl glycolate; and of vinyl butyrate with monoallyl glutarate; together with hexamethylol melamine hexamethyl ether, methylated or ethylated urea/formaldehyde condensates or methylated melamine/formaldehyde condensates and toluene sulphonic acid; or epichlorhydrin/diphenylolpropane condensates and tertiary amines.